CN109906204B - Reverse osmosis membrane treatment system and reverse osmosis membrane treatment method - Google Patents

Reverse osmosis membrane treatment system and reverse osmosis membrane treatment method Download PDF

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CN109906204B
CN109906204B CN201780067202.XA CN201780067202A CN109906204B CN 109906204 B CN109906204 B CN 109906204B CN 201780067202 A CN201780067202 A CN 201780067202A CN 109906204 B CN109906204 B CN 109906204B
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reverse osmosis
osmosis membrane
water
treatment
permeate
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CN109906204A (en
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中村勇规
高田明广
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Organo Corp
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/08—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/12—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/12—Addition of chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/025—Permeate series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2181—Inorganic additives
    • B01D2323/21815—Acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

A reverse osmosis membrane treatment system and a reverse osmosis membrane treatment method are provided for performing treatment by a reverse osmosis membrane having two or more stages, whereby a sufficient water quality improvement effect can be obtained. The reverse osmosis membrane treatment system 1 is provided with: a first reverse osmosis membrane treatment device 12 in which water to be treated passes through a first reverse osmosis membrane to obtain first permeate water and first concentrate water; and at least one second reverse osmosis membrane treatment unit 14, wherein the first permeate water is passed through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water. The permeate flux per 1MPa effective pressure of the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure of the second reverse osmosis membrane is 0.5m3/m2And/d is as follows.

Description

Reverse osmosis membrane treatment system and reverse osmosis membrane treatment method
Technical Field
The present invention relates to a reverse osmosis membrane treatment system and a reverse osmosis membrane treatment method.
Background
A reverse osmosis membrane treatment system and a reverse osmosis membrane treatment method using a reverse osmosis membrane have hitherto been known, in which treatment target water (such as industrial water or city water) is treated with a reverse osmosis membrane to obtain permeate water (treated water) and concentrate water.
It is known that in the reverse osmosis membrane treatment system and the reverse osmosis membrane treatment method using a reverse osmosis membrane for treatment as described above, using two or more stages of reverse osmosis membrane units in which the membranes are the same, a membrane having an improved rejection by using a rejection improver is used as the second reverse osmosis membrane for the purpose of improving water quality.
For example, patent document 1 discloses a pure water production apparatus including: a first stage reverse osmosis membrane device through which the treatment target water passes; and a second-stage reverse osmosis membrane separation device through which the permeated water from the first-stage reverse osmosis membrane separation device passes, wherein at least the reverse osmosis membrane device in the second stage is provided with a reverse osmosis membrane treated with a rejection improving agent which is a compound having a polyalkylene glycol chain, such as polyethylene glycol.
However, the method according to patent document 1 cannot obtain a sufficient water quality improvement effect.
Documents of the prior art
Patent document
Patent document 1 JP 2008-161818A
Disclosure of Invention
An advantage of the present invention is to provide a reverse osmosis membrane treatment system and a reverse osmosis membrane treatment method for performing treatment by a reverse osmosis membrane having two or more stages, whereby a sufficient water quality improvement effect can be obtained.
The invention provides a reverse osmosis membrane treatment system, comprising: a first reverse osmosis membrane treatment unit for treatingPassing the target water through a first reverse osmosis membrane to obtain a first permeate water and a first concentrate water; and at least one second reverse osmosis membrane treatment unit for passing the first permeate water through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water, wherein the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is 0.5m3/m2And/d is as follows.
In the reverse osmosis membrane treatment system, the second reverse osmosis membrane is preferably a membrane modified with an oxidizing agent.
In the reverse osmosis membrane treatment system, the second reverse osmosis membrane is preferably a membrane modified with at least one of a stabilized hypobromous acid composition comprising a bromine-based oxidizing agent and a sulfamic acid compound and a stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and a sulfamic acid compound.
In the reverse osmosis membrane treatment system, the treatment target water preferably contains at least any one of boron and a low molecular weight organic substance having a molecular weight of 200 or less.
In addition, the invention also provides a reverse osmosis membrane treatment method, which comprises the following steps: a first reverse osmosis membrane treatment step of passing treatment target water through a first reverse osmosis membrane to obtain first permeate water and first concentrate water; and at least one second reverse osmosis membrane treatment step of passing the first permeate water through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water, wherein the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is 0.5m3/m2And/d is as follows.
In the reverse osmosis membrane treatment method, the second reverse osmosis membrane is preferably a membrane modified with an oxidizing agent.
In the reverse osmosis membrane treatment process, the second reverse osmosis membrane is preferably a membrane modified with at least one of a stabilized hypobromous acid composition comprising a bromine-based oxidizing agent and a sulfamic acid compound and a stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and a sulfamic acid compound.
In the reverse osmosis membrane treatment method, the treatment target water preferably contains at least any one of boron and a low molecular weight organic substance having a molecular weight of 200 or less.
In a reverse osmosis membrane treatment system and a treatment method for performing treatment by a reverse osmosis membrane having two or more stages, a sufficient water quality improvement effect can be obtained.
Drawings
Fig. 1 is a schematic block diagram showing one example of a reverse osmosis membrane treatment system according to an embodiment of the present invention.
Fig. 2 is a schematic block diagram showing one example of a water treatment system including a reverse osmosis membrane treatment system according to an embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described below. This embodiment is an example of the practice of the invention, and the invention is not limited to this embodiment.
An example of a reverse osmosis membrane treatment system according to an embodiment of the present invention is schematically shown in fig. 1, and the configuration of the reverse osmosis membrane treatment system will be described.
The reverse osmosis membrane treatment system 1 includes: a first reverse osmosis membrane treatment device 12 as a first reverse osmosis membrane treatment unit for passing treatment target water through a first reverse osmosis membrane to obtain first permeate water and first concentrate water; and a second reverse osmosis membrane treatment device 14 as a second reverse osmosis treatment unit for passing the first permeate water through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water. Here, the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is 0.5m3/m2And/d is as follows. The reverse osmosis membrane treatment system 1 may include a treatment target water tank 10 for storing treatment target water.A first permeate tank for storing the first permeate may be provided between the first reverse osmosis membrane treatment device 12 and the second reverse osmosis membrane treatment device 14.
In the reverse osmosis membrane treatment system 1 of fig. 1, a treatment target water pipe 18 is connected to an inlet of a treatment target water tank 10, and an outlet of the treatment target water tank 10 and an inlet of a first reverse osmosis membrane treatment device 12 are connected to each other through a treatment target water supply pipe 20 via a pump 16. The first permeate outlet of the first reverse osmosis membrane treatment device 12 and the inlet of the second reverse osmosis membrane treatment device 14 are connected to each other by a first permeate pipe 22. The first concentrated water pipe 24 is connected to a first concentrated water outlet of the first reverse osmosis membrane treatment device 12. A second permeate pipe 26 and a second concentrate pipe 28 are connected to the first permeate outlet and the second concentrate outlet of the second reverse osmosis membrane treatment device 14, respectively. The oxidizer-adding pipe 30 may be connected to the first permeate pipe 22 as an oxidizer-adding unit for adding an oxidizer.
The reverse osmosis membrane treatment method and the operation of the reverse osmosis membrane treatment system 1 according to this embodiment will be described below.
The treatment target water as an object to be treated is stored in the treatment target water tank 10 through the treatment target water pipe 18 as necessary. The treatment target water is supplied to the first reverse osmosis membrane treatment device 12 through the treatment target water supply pipe 20 by the pump 16, and the first reverse osmosis membrane treatment of the treatment target water is performed in the first reverse osmosis membrane treatment device 12 (first reverse osmosis membrane treatment step). The first permeate water obtained by the first reverse osmosis membrane treatment is supplied to the second reverse osmosis membrane treatment device 14 through the first permeate pipe 22. In the first permeated water pipe 22, an oxidizing agent as a modifier may be added to the first permeated water through the oxidizing agent adding pipe 30 as needed (oxidizing agent adding step). After the oxidizing agent is added as necessary, second reverse osmosis membrane treatment of the first permeate water is performed in the second reverse osmosis membrane treatment device 14 (second reverse osmosis membrane treatment step). At least a part of the first permeate water obtained by the first reverse osmosis membrane treatment may be recycled to the feed water of the first reverse osmosis membrane treatment device 12, for example, to the treatment target water tank 10. The first concentrated water obtained by the first reverse osmosis membrane treatment may be discharged through the first concentrated water pipe 24, or at least partially recycled to the supply water of the first reverse osmosis membrane treatment device 12, for example, to the treatment target water tank 10. The second permeate water obtained by the second reverse osmosis membrane treatment may be discharged through the second permeate pipe 26, or at least partially recycled to the feed water of the first reverse osmosis membrane treatment device 12 of the preceding stage (for example, recycled to the treatment target water tank 10), or at least partially recycled to the feed water of the second reverse osmosis membrane treatment device 14, for example, recycled to the first permeate pipe 22. The second concentrated water obtained by the second reverse osmosis membrane treatment may be discharged through the second concentrated water pipe 28, or at least partially recycled to the feed water of the first reverse osmosis membrane treatment device 12 of the preceding stage, for example, to the treatment target water tank 10, or at least partially recycled to the feed water of the second reverse osmosis membrane treatment device 14, for example, to the first permeate pipe 22. A pump may be provided in the first permeate tube 22 for repressurization. The oxidizing agent may be added to the first permeate pipe 22, and may be added to the suction side or the discharge side of a pump provided in the first permeate pipe 22. A pH adjusting agent may be added to the first permeate water in the first reverse osmosis membrane treatment apparatus 12. A degassing membrane apparatus as a degassing unit may be provided between the first reverse osmosis membrane treatment apparatus 12 and the second reverse osmosis membrane treatment apparatus 14 to subject the first permeate water to a degassing treatment. At least one of a free chlorine or total chlorine measuring unit, a pH measuring unit, an inorganic carbon concentration (IC) measuring unit, and the like may be provided between the first reverse osmosis membrane treatment device 12 and the second reverse osmosis membrane treatment device 14, or in the second concentrate water pipe 28.
In the reverse osmosis membrane treatment system 1, at least one reverse osmosis membrane treatment device (a third reverse osmosis membrane treatment device, a fourth reverse osmosis membrane treatment device as needed, and/or an additional subsequent reverse osmosis membrane treatment device) may be further provided on the second permeate side of the second reverse osmosis membrane treatment device 14 for the purpose such as improving the quality of the permeate water. In this case, it is preferable that the permeate flux per 1MPa of effective pressure in the reverse osmosis membrane used after the second reverse osmosis membrane treatment is lower than that in the first reverse osmosis membrane per 1MPaThe permeate flux per 1MPa effective pressure in the reverse osmosis membrane used after the second reverse osmosis membrane treatment is 0.5m3/m2And/d is as follows.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, the treatment is performed by the reverse osmosis membrane in two or more stages, the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is 0.5m3/m2And/d is as follows. The inventors carefully studied the relationship between the rejection rate of low molecular weight organic substances and the permeation flux per 1MPa effective pressure in the second reverse osmosis membrane, and found that there is a secondary correlation. Here, the permeation flux (═ 0.5 m) per 1MPa effective pressure is due to3/m2D) forms an inflection point, so a reverse osmosis membrane having a high rejection rate (i.e. "permeate flux per 1MPa effective pressure is 0.5 m)3/m2A reverse osmosis membrane below/d ") as the reverse osmosis membrane of the second stage. Effective pressure per 1MPa "/d or less" is used as a reverse osmosis membrane in the second pass. When the additional reverse osmosis membrane treatment device of the third and subsequent stages is provided on the second permeate water side, it is preferable that the permeate flux per 1MPa effective pressure in each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux per 1MPa effective pressure in each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is 0.5m3/m2And/d is as follows. Therefore, in the reverse osmosis membrane treatment system and the treatment method for performing treatment by a reverse osmosis membrane having two or more stages, a sufficient water quality improvement effect can be obtained. Preferably, the first reverse osmosis membrane is "a permeate flux per 1MPa of effective pressure greater than 0.5m3/m2The reverse osmosis membrane of/d, and the second reverse osmosis membrane or each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is a reverse osmosis membrane having a high rejection rate, i.e. "permeate flux per 1MPa effective pressure is 0.5m3/m2A ratio of d or lessA reverse osmosis membrane ".
The permeate flux per 1MPa effective pressure of each reverse osmosis membrane used in the second reverse osmosis membrane or in the second and subsequent reverse osmosis membrane treatments was 0.5m3/m2A value of less than d, preferably 0.4m3/m2And/d is as follows. If the permeate flux per 1MPa effective pressure of each reverse osmosis membrane used in the second reverse osmosis membrane or in the second and subsequent reverse osmosis membrane treatments is greater than 0.5m3/m2And d, the quality of the produced treated water deteriorates.
The permeate flux per 1MPa effective pressure of the second reverse osmosis membrane or each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is not limited as long as it is lower than the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane, and for example, the permeate flux per 1MPa effective pressure of the second reverse osmosis membrane or each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is in the range of 10% to 60%, preferably 15% to 45%, of the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane. If the permeate flux per 1MPa effective pressure of the second reverse osmosis membrane or each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is equal to or higher than the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane, deterioration of the quality of the produced treated water is caused.
In the reverse osmosis membrane treatment method and the treatment system according to this embodiment, each of the second reverse osmosis membrane, preferably the second reverse osmosis membrane and the following reverse osmosis membrane is preferably a membrane modified with an oxidizing agent as a modifier. When the membrane modified with the oxidizing agent is used as a reverse osmosis membrane having a high rejection rate, the water quality can be further improved. In order to obtain a membrane modified with an oxidizing agent, the modifying agent is brought into contact with the reverse osmosis membrane by adding the modifying agent to water, washing water, or the like supplied to the reverse osmosis membrane, or the reverse osmosis membrane may be immersed in water containing the modifying agent.
The oxidizing agent is not particularly limited as long as it has an oxidizing action, and examples thereof include chlorine-based oxidizing agents, bromine-based oxidizing agents, stable hypochlorous acid compositions, and stable hypobromous acid compositions.
Examples of chlorine-based oxidizing agents include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, and chloroisocyanuric acid or a salt thereof. Among the above compounds, examples of the salt include: alkali metal salts of hypochlorous acid, such as sodium hypochlorite and potassium hypochlorite; alkaline earth metal salts of hypochlorous acid, such as calcium hypochlorite and barium hypochlorite; alkali metal salts of chlorous acid such as sodium chlorite and potassium chlorite; alkaline earth metal salts of chlorous acid, such as barium chlorite; metal salts of chlorous acid, such as nickel chlorous acid; alkali metal salts of chloric acid such as ammonium chlorate, sodium chlorate, and potassium chlorate; and alkaline earth metal salts of chloric acid, such as calcium chlorate and barium chlorate. These chlorine-based oxidizing agents may be used alone or in combination of two or more. From the viewpoint of workability, sodium hypochlorite is preferably used as the chlorine-based oxidizing agent.
Examples of bromine-based oxidizing agents include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromous acid. Hypobromous acid can be prepared by reacting a bromide (e.g., sodium bromide) with a chlorine-based oxidizing agent (e.g., hypochlorous acid).
A stable hypochlorous acid composition includes a chlorine-based oxidizing agent and an sulfamic acid compound. The "stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and an aminosulfonic acid compound" may be a stabilized hypochlorous acid composition comprising a mixture of the "chlorine-based oxidizing agent" and the "aminosulfonic acid compound", or a stabilized hypochlorous acid composition comprising a reaction product of the "chlorine-based oxidizing agent" and the "aminosulfonic acid compound".
A stable hypobromous acid composition includes a bromine-based oxidizing agent and an aminosulfonic acid compound. The "stabilized hypobromous acid composition comprising a bromo oxidizing agent and an aminosulfonic acid compound" may be a stabilized hypobromous acid composition comprising a mixture of a "bromo oxidizing agent" and an "aminosulfonic acid compound", or a stabilized hypobromous acid composition comprising a reaction product of a "bromo oxidizing agent" and an "aminosulfonic acid compound".
Among the above oxidizing agents, the oxidizing agent is preferably a stabilized hypochlorous acid composition or a stabilized hypobromous acid composition, more preferably a stabilized hypobromous acid composition. The stabilized hypochlorous acid composition or the stabilized hypobromous acid composition exhibits slime-inhibiting effect and modification effect equal to or higher than those of chlorine-based oxidizing agents (such as hypochlorous acid), but has a lower influence on the deterioration of the reverse osmosis membrane than those of chlorine-based oxidizing agents, so that the deterioration of the membrane due to repeated modification can be inhibited. Therefore, a stable hypochlorous acid composition or a stable hypobromous acid composition used in the reverse osmosis membrane treatment method and treatment system according to this embodiment is suitable as the modifier.
Therefore, in the reverse osmosis membrane treatment method and treatment system according to this embodiment, the second reverse osmosis membrane or each reverse osmosis membrane used in the second and subsequent reverse osmosis membrane treatments is preferably a membrane modified by at least one of a stabilized hypobromous acid composition comprising a bromine-based oxidizing agent and a sulfamic acid compound and a stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and a sulfamic acid compound.
If the "bromine-based oxidizing agent" is bromine in the reverse osmosis membrane treatment method and treatment system according to this embodiment, the deterioration effect on the reverse osmosis membrane may be very low due to the absence of the chlorine-based oxidizing agent, and slime inhibiting effect and modification effect on the reverse osmosis membrane may be exhibited. When a chlorine-based oxidizing agent is included, chloric acid may be generated.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, for example, a mixture of the "bromine-based oxidizing agent" and the "sulfamic acid compound" or a mixture of the "chlorine-based oxidizing agent" and the "sulfamic acid" is present as a modifier in the feed water or the like of the reverse osmosis membrane. Thus, a stable hypobromous acid composition or a stable hypochlorous acid composition can be generated in the treatment target water.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, for example, a stabilized hypobromous acid composition (which is "a reaction product of a bromine-based oxidizing agent and an aminosulfonic acid compound") or a stabilized hypochlorous acid composition (which is "a reaction product of a chlorine-based oxidizing agent and an aminosulfonic acid compound") may be present as a modifier in the feed water or the like of the reverse osmosis membrane.
Specifically, in the reverse osmosis membrane treatment method and treatment system according to this embodiment, for example, "bromine", "bromine chloride", "hypobromous acid" or a mixture of "a reaction product of sodium bromide with hypochlorous acid" and "an aminosulfonic acid compound" may be present as a modifier in the feed water or the like of the reverse osmosis membrane. Alternatively, a mixture of "hypochlorous acid" and "sulfamic acid compound" may be present as a modifier in the feed water or the like of the reverse osmosis membrane.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, for example, a stable hypobromous acid composition, which is "a reaction product of bromine and an aminosulfonic acid compound", "a reaction product of bromine chloride and an aminosulfonic acid compound", "a reaction product of hypobromous acid and an aminosulfonic acid compound", or "a reaction product of an aminosulfonic acid compound with a reaction product of sodium bromide and hypochlorous acid", may be present as a modifier in the feed water or the like of the reverse osmosis membrane. Alternatively, a stable hypochlorous acid composition which is a "reaction product of hypochlorous acid and an aminosulfonic acid compound" may be present as a modifier in the feed water or the like of the reverse osmosis membrane.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, the oxidizing agent is contacted with the reverse osmosis membrane, preferably in a pH range of 3 to 12, more preferably in a pH range of 4 to 9. If the oxidizing agent is contacted with the reverse osmosis membrane at a pH of less than 3, the rejection rate may decrease due to the occurrence of deterioration of the reverse osmosis membrane in the case where the oxidizing agent is contacted with the reverse osmosis membrane for a long time, while the modification effect may be insufficient if the oxidizing agent is contacted with the reverse osmosis membrane at a pH of more than 12. In particular, when the oxidizing agent is contacted with the reverse osmosis membrane in the pH range of 4 to 9, the quality of the permeated water from the reverse osmosis membrane can be sufficiently improved while suppressing the deterioration of the reverse osmosis membrane. In order to bring the modifier into contact with the reverse osmosis membrane within the above pH range, for example, the pH of feed water or the like of the reverse osmosis membrane may be maintained within the above range, or the pH of a liquid in which the reverse osmosis membrane is immersed may be maintained within the above range.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, for example, in operating a reverse osmosis membrane plant containing a reverse osmosis membrane, the "bromine-based oxidizing agent" or the "chlorine-based oxidizing agent" and the "sulfamic acid compound" may be injected into the feed water or the like of the reverse osmosis membrane by a chemical injection pump or the like. The "bromine-based oxidizing agent" or the "chlorine-based oxidizing agent" and the "sulfamic acid compound" may be added separately to the feed water or the like, or may be added in the form of a stock solution to the feed water or the like of the reverse osmosis membrane after being mixed together. For example, the modifying agent is contacted with the reverse osmosis membrane by immersing the reverse osmosis membrane in water containing a "bromine-based oxidizing agent" or a "chlorine-based oxidizing agent" and a "sulfamic acid compound" for a predetermined period of time.
For example, the "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound" or the "reaction product of a chlorine-based oxidizing agent and a sulfamic acid compound" may be injected into the feed water or the like of the reverse osmosis membrane by a chemical injection pump or the like. For example, the modifier is contacted with the reverse osmosis membrane by immersing the reverse osmosis membrane in water containing a "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound" or a "reaction product of a sulfamic acid compound and a reaction product of a bromine compound and a chlorine-based oxidizing agent" for a predetermined period of time.
In order to carry out the modification by the oxidizing agent, the oxidizing agent may be continuously or intermittently added to the feed water, the washing water, etc. of the reverse osmosis membrane when the reverse osmosis membrane apparatus containing the reverse osmosis membrane is operated, or the oxidizing agent may be continuously or intermittently added to the feed water, the washing water, etc. of the reverse osmosis membrane or the reverse osmosis membrane may be immersed in the water containing the oxidizing agent when the rejection rate of the reverse osmosis membrane is lowered.
The oxidizing agent may be contacted with the reverse osmosis membrane under a standard atmospheric pressure condition, a pressurized condition or a reduced pressure condition, but it is preferable to contact the oxidizing agent with the reverse osmosis membrane under a pressurized condition because the modification can be performed without stopping the reverse osmosis membrane apparatus, and the modification of the reverse osmosis membrane and the like can be reliably performed. Preferably, the oxidizing agent may be contacted with the reverse osmosis membrane under pressurized conditions, for example, between 0.1MPa and 8.0 MPa.
The oxidizing agent may be contacted with the reverse osmosis membrane at a temperature of, for example, 5 ℃ to 35 ℃.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" or the "chlorine-based oxidizing agent" is preferably 1 or more, more preferably 1 or more and 2 or less. When the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" or the "chlorine-based oxidizing agent" is less than 1, the reverse osmosis membrane may be deteriorated, and when the ratio is more than 2, the production cost may be increased.
The total concentration of chlorine in contact with the reverse osmosis membrane is preferably 0.01 to 100mg/L in terms of effective chlorine concentration. When the total concentration of chlorine is less than 0.01mg/L, a sufficient modification effect may not be obtained, and when the total concentration of chlorine is more than 100mg/L, deterioration of the reverse osmosis membrane or corrosion of piping and the like may occur.
The formulation of "bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)" or the formulation of "reaction product of bromine and sulfamic acid compound" in which bromine is used is more preferable as the modifier because the amount of by-product bromic acid can be lower and the reverse osmosis membrane is less deteriorated as compared with the formulation of "hypochlorous acid, bromine compound and sulfamic acid", the formulation of "bromine chloride and sulfamic acid", and the like.
That is, in the reverse osmosis membrane treatment method and treatment system according to this embodiment, it is preferable that bromine and a sulfamic acid compound (a mixture of bromine and a sulfamic acid compound) are present in the feed water or the like of the reverse osmosis membrane. Preferably, the reaction product of bromine and the sulfamic acid compound is present in feed water or the like of the reverse osmosis membrane.
Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Among them, sodium bromide is preferred from the viewpoint of production cost.
The sulfamic acid compound is a compound represented by the following general formula (1).
R2NSO3H (1)
(wherein each R independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
Examples of the sulfamic acid compound include: sulfamic acid (amidosulfuric acid) where both R groups are hydrogen atoms; sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other R group is an alkyl group having 1 to 8 carbon atoms, such as N-methylaminosulfonic acid, N-ethylaminosulfonic acid, N-propylaminosulfonic acid, N-isopropylaminosulfonic acid and N-butylaminosulfonic acid; sulfamic acid compounds in which both R groups are alkyl groups having 1 to 8 carbon atoms, such as N, N-dimethylaminosulfonic acid, N-diethylaminosulfonic acid, N-dipropylaminosulfonic acid, N-dibutylaminosulfonic acid, N-methyl-N-ethylaminosulfonic acid, and N-methyl-N-propylsulfamic acid; sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other R group is an aryl group having 6 to 10 carbon atoms, such as N-phenyl sulfamic acid; and salts of the above compounds. Examples of sulfamates include: alkali metal salts, such as sodium and potassium salts; alkaline earth metal salts such as calcium, strontium and barium salts; other metal salts such as manganese salts, copper salts, zinc salts, iron salts, cobalt salts and nickel salts; and ammonium and guanidinium salts. The sulfamic acid compound and its salt may be used alone or in combination of two or more. From the viewpoint of environmental load and the like, sulfamic acid (amidosulfuric acid) is preferably used as the sulfamic acid compound.
In the reverse osmosis membrane treatment method and treatment system according to this embodiment, when at least one of the stabilized hypobromous acid composition and the stabilized hypochlorous acid composition is present as a modifier in the feed water or the like of the reverse osmosis membrane, an alkali may also be present. Examples of the base include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of production stability at low temperature, etc., sodium hydroxide and potassium hydroxide may be used in combination. The base may be used in the form of an aqueous solution rather than as a solid.
The reverse osmosis membrane treatment method and treatment system according to this embodiment can be applied to a cellulose acetate membrane or a polyamide-based polymer membrane which is currently mainstream. The polyamide-based polymer film has relatively low resistance to an oxidizing agent, and thus when free chlorine or the like is continuously brought into contact with the polyamide-based polymer film, the film performance is remarkably deteriorated. However, in the reverse osmosis membrane treatment method and the treatment system according to this embodiment, the polyamide-based polymer membrane may hardly undergo such a significant deterioration in membrane performance even.
Each of the reverse osmosis membranes used in the second and subsequent reverse osmosis membrane treatments had a lower permeate flux per 1MPa of effective pressure than that used in the first reverse osmosis membrane treatment, with significantly improved barrier properties. "in each of the second and subsequent reverse osmosis membrane treatments, the permeation flux per 1MPa effective pressure used was 0.5m3/m2A reverse osmosis membrane "below/d, the permeate flux per 1MPa effective pressure used in the first reverse osmosis membrane treatment is greater than 0.5m per reverse osmosis membrane used in the second reverse osmosis membrane treatment3/m2A reverse osmosis membrane of/d. "permeate flux per 1MPa effective pressure of 0.5 m" was used in the second reverse osmosis membrane treatment3/m2A reverse osmosis membrane below d ", the quality of the treated water in the second stage reverse osmosis membrane unit can be significantly higher than when" the permeate flux per 1MPa of effective pressure is more than 0.5m3/m2Quality of treated water in conventional two-stage reverse osmosis membrane system of reverse osmosis membrane of/d ".
The permeate flux was obtained by dividing the amount of permeate water by the membrane area. The "effective pressure" is an effective pressure acting on the membrane, which is measured by a pressure measured from JIS K3802: the permeate pressure difference and the secondary pressure are subtracted from the average operating pressure specified in "membrane terminology" in 2015. The average operating pressure is an average of the pressure of feed water of the membrane (operating pressure) and the pressure of concentrate water (concentrate outlet pressure) at the primary side of the membrane, and is given by the following equation.
Average operating pressure (operating pressure + outlet pressure of concentrated water)/2
The permeate flux per 1MPa effective pressure can be calculated from data described in the membrane manufacturer's manual, e.g., the amount of permeate water, membrane area, recovery in the evaluation, NaCl concentration, etc. When several membranes having the same permeation flux are loaded in one or more pressure vessels, the permeation flux of each loaded membrane can be calculated from data such as the average operating pressure/secondary pressure in the pressure vessel, the quality of raw water, the amount of permeate water, and the number of membranes.
A reverse osmosis membrane usable as the reverse osmosis membrane of the second reverse osmosis membrane treatment or each of the second and subsequent reverse osmosis membrane treatments and having a permeate flux of 0.5m per 1MPa of effective pressure3/m2Examples of the film of/d include: SWC series (Hydranautics), TM800 series (Dongli), SW30 series (DOW) and HR-RO series (chestnut field industry). Specific examples thereof include: SWC5MAX (permeate flux per 1MPa effective pressure: 0.32m3/m2D) (Hydranautics), SWC6MAX (permeate flux per 1MPa effective pressure: 0.43m3/m2D) (Hydranautics), SW30ULE (permeate flux per 1MPa effective pressure: 0.39m3/m2D) (DOW), SW30HRLE (permeate flux per 1MPa effective pressure: 0.25m3/m2D) (DOW), TM820V (permeate flux per 1MPa effective pressure: 0.32m3/m2D) (Dongli), TM820K (permeation flux per 1MPa effective pressure: 0.20m3/m2D) (Dongli) and HR-RO (permeation flux per 1MPa effective pressure: 0.36m3/m2D) (chestnut field industry).
Examples of membranes that have a higher permeate flux per 1MPa effective pressure than the reverse osmosis membrane of the second reverse osmosis membrane treatment or the reverse osmosis membranes of each of the second and subsequent reverse osmosis membrane treatments and that can be used as the first reverse osmosis membrane include: ES20-D8 (permeation flux per 1MPa effective pressure: 1.14m3/m2D) (Dendo electrician), LFC3-LD (permeation flux per 1MPa effective pressure: 0.79m3/m2D) (Hydranautics), BW30XFR (permeation flux per 1MPa effective pressure: 0.84m3/m2D) (DOW) and TML20-D (permeate flux per 1MPa effective pressure: 0.78m3/m2/d) (Dongli).
The membrane shape of the reverse osmosis membrane is not particularly limited, and examples thereof include a tubular type, a flat membrane type, a spiral wound type, and a hollow fiber type, and the spiral wound type may be any one of a 4-inch element type, an 8-inch element type, a 16-inch element type, and the like.
The first reverse osmosis membrane treatment device 12, the second reverse osmosis membrane treatment device 14, and the reverse osmosis membrane treatment device subsequent to the second reverse osmosis membrane treatment device may each include a plurality of modules. That is, the feed water may be supplied to each of the plurality of modules of each reverse osmosis membrane device, or the concentrated water in one module may be used as the feed water of the next module (christmas tree system).
The dispersant may be used in combination with an antibacterial agent to prevent scaling in the case where scale is generated when the pH of treatment target water in a reverse osmosis membrane apparatus is 7 or more. Examples of the dispersant include: polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant added to the treatment target water is, for example, in the range of 0.1 to 1000mg/L in terms of concentration in the RO concentrated water.
In order to prevent scaling without using a dispersant, for example, the operating conditions (e.g., recovery rate) of the reverse osmosis membrane apparatus are adjusted so that the silica concentration in the RO concentrated water is equal to or less than the solubility of silica, and the Langelier saturation index, which is an index of calcium scaling, is 0 or less.
Examples of applications of the reverse osmosis membrane apparatus include: a primary pure water system for ultrapure water production, wastewater recovery and the like. Regarding these applications, the reverse osmosis membrane apparatus can be suitably used for treating treatment target water containing at least one of boron and low molecular weight organic substances having a molecular weight of 200 or less, which are difficult to achieve by using "permeation flux per 1MPa effective pressure of more than 0.5m3/m2The reverse osmosis membrane of/d "conventional two-stage reverse osmosis membrane apparatus. Examples of the low molecular weight organic substance having a molecular weight of 200 or less include: alcohol compounds such as methanol, ethanol, and isopropyl alcohol (IPA); amine compounds such as monoethanolamine and urea; and tetraalkylammonium salts such as tetramethylammonium hydroxide.
< Water treatment System >
In the reverse osmosis membrane treatment method and the treatment system according to this embodiment, the treatment target water is preferably pretreated water treated in advance in pretreatment as shown in fig. 2.
For example, as shown in fig. 2, the water treatment system 3 includes a reverse osmosis membrane treatment system 1, and includes a pretreatment system 50 before the reverse osmosis membrane treatment system 1. The water treatment system 3 may include a pre-treatment tank 52 if desired.
In the water treatment system 3, a raw water supply pipe 54 is connected to an inlet of the pretreatment system 50, and an outlet of the pretreatment system 50 is connected to an inlet of the pretreatment water tank 52 through a pretreatment water pipe 56. An outlet of the pretreatment water tank 52 is connected to an inlet of the reverse osmosis membrane treatment system 1 through a pretreatment water supply pipe 58. For example, the pretreated water supply pipe 58 is connected to the treatment target water pipe 18 of the reverse osmosis membrane treatment system 1.
The oxidizer-adding pipe 30 for adding an oxidizer as a modifier may be connected to the raw water-supplying pipe 54 as an oxidizer-adding pipe 30a, to the pretreatment system 50 as an oxidizer-adding pipe 30b, to the pretreatment water pipe 56 as an oxidizer-adding pipe 30c, to the pretreatment water tank 52 as an oxidizer-adding pipe 30d, to the pretreatment water-supplying pipe 58 as an oxidizer-adding pipe 30e, and to the reverse osmosis membrane treatment system 1 as an oxidizer-adding pipe 30 f.
In the water treatment system 3, raw water is supplied to the pretreatment system 50 through the raw water supply pipe 54, and pretreatment (pretreatment step) as described below is performed in the pretreatment system 50. The pretreated water subjected to the pretreatment is stored in the pretreated water tank 52 through the pretreated water pipe 56 as required, and then supplied to the reverse osmosis membrane treatment system 1 through the pretreated water supply pipe 58. In the reverse osmosis membrane treatment system 1, the reverse osmosis membrane treatment is performed twice or more (reverse osmosis membrane treatment step) as described above.
The oxidizing agent as the modifier may be added to any one of the raw water, the pretreated water, and the treatment target water, to the raw water supply pipe 54 through the oxidizing agent addition pipe 30a, and/or to the pretreatment system 50 through the oxidizing agent addition pipe 30b, and/or to the pretreated water pipe 56 through the oxidizing agent addition pipe 30c, and/or to the pretreated water tank 52 through the oxidizing agent addition pipe 30d, and/or to the pretreated water supply pipe 58 through the oxidizing agent addition pipe 30e, and/or to the reverse osmosis membrane treatment system 1 through the oxidizing agent addition pipe 26 f.
In the pretreatment step, biological, physical or chemical pretreatment such as biological treatment, flocculation and precipitation treatment, dissolved air flotation treatment, filtration treatment, membrane separation treatment, activated carbon treatment, ozone treatment, ultraviolet irradiation treatment, softening treatment or decarburization treatment, or a combination of these pretreatments is carried out as necessary.
In the reverse osmosis membrane treatment system 1, if necessary, a total chlorine concentration measuring device, a pump, a safety filter, a flow meter, a pressure gauge, a thermometer, an Oxidation Reduction Potential (ORP) meter, a residual chlorine meter, a conductivity meter, a pH meter, an energy recovery device, and the like may be provided in addition to the reverse osmosis membrane in the system.
For the post-treatment (post-treatment step) in the reverse osmosis membrane treatment system 1, a regenerated ion exchange resin device, an electrodeionization treatment device (EDI), a non-regenerated ion exchange resin device, a degassing membrane treatment device, an ultraviolet sterilization device, an ultraviolet oxidation device, a heating device, an ultrafiltration device, and the like may be provided.
In the water treatment system 3, a dispersant other than the oxidizing agent and an antibacterial agent, a pH adjusting agent, and the like may be added to at least one of the raw water, the pretreated water, and the treatment target water in at least one of the raw water supply pipe 54, the pretreatment system 50, the pretreatment water pipe 56, the pretreatment water tank 52, the pretreatment water supply pipe 58, and the reverse osmosis membrane treatment system 1.
< reverse osmosis membrane modifier >
The reverse osmosis membrane modifier according to this embodiment comprises a stabilized hypobromous acid composition or a stabilized hypochlorous acid composition, which may further comprise a base, wherein the stabilized hypobromous acid composition or the stabilized hypochlorous acid composition comprises a mixture of a "bromine-based oxidizing agent or a chlorine-based oxidizing agent" and a "sulfamic acid compound".
The modifying agent according to this embodiment comprises a stabilized hypobromous acid composition or a stabilized hypochlorous acid composition, which comprises a reaction product of a bromine-based oxidizing agent and an aminosulfonic acid compound, and may further comprise a base.
The bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent and sulfamic acid compound are as described above.
Examples of commercially available stabilized hypochlorous acid compositions comprising a chlorine-based oxidizing agent and a sulfamic acid compound include "kuriver IK-110" manufactured by chestnut field industry.
The modifying agent according to this embodiment is preferably a mixture comprising bromine and a sulfamic acid compound (comprising a mixture of bromine and sulfamic acid compounds), such as a mixture of bromine, sulfamic acid compound, base and water; or a reaction product comprising bromine and a sulfamic acid compound, such as a mixture of a reaction product of bromine and a sulfamic acid compound, a base, and water.
In the modifier according to this embodiment, the slime inhibitor including the stabilized hypobromous acid composition containing the bromine-based oxidizing agent and the sulfamic acid compound, in particular, the slime inhibitor including the stabilized hypobromous acid composition containing the bromine and the sulfamic acid compound has a higher oxidizing ability and a higher modifying effect, slime inhibiting ability and slime separating ability than the modifier containing the chlorine-based oxidizing agent and the sulfamic acid compound (chloroaminosulfonic acid or the like), but hardly causes significant film deterioration as caused by hypochlorous acid having a relatively high oxidizing ability. At standard use concentrations, the membrane degradation effect can be substantially neglected. Therefore, the above slime inhibitor is most suitable as a modifier.
Unlike hypochlorous acid, the modifier according to this embodiment hardly permeates a reverse osmosis membrane, and thus hardly affects the quality of treated water. In addition, the concentration can be measured on site as with hypochlorous acid or the like, so that the concentration can be controlled more accurately.
The pH of the modifier is for example greater than 13.0, more preferably greater than 13.2. When the pH of the modifier is 13.0 or less, the available halogen in the modifier may be unstable.
The concentration of bromic acid in the modifier is preferably less than 5 mg/kg. When the concentration of bromic acid in the modifier is 5mg/kg or more, the concentration of bromate ions in the RO permeate water may increase.
< method for producing modifier >
The modifier according to this embodiment is obtained by mixing a bromine-based oxidizing agent or a chlorine-based oxidizing agent with a sulfamic acid compound, and may also be mixed with a base.
Preferably, the process for preparing a modifier comprising a stabilized hypobromous acid composition comprising bromine and a sulfamic acid compound comprises: a step of adding bromine to a mixed liquid containing water, a base and a sulfamic acid compound in an inert gas atmosphere to carry out a reaction, or a step of adding bromine to a mixed liquid containing water, a base and a sulfamic acid compound in an inert gas atmosphere. The concentration of bromate ions in the modifier is reduced by adding bromine in an inert gas atmosphere for reaction or adding bromine in the inert gas atmosphere, so that the concentration of bromate ions in RO permeate water can be reduced.
The inert gas to be used is not limited, but at least one of nitrogen and argon is preferable from the viewpoint of production and the like, and nitrogen is particularly preferable from the viewpoint of production cost and the like.
The oxygen concentration in the reaction vessel at the time of adding bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reaction vessel is more than 6% while the bromine is being reacted, the amount of the generated bromic acid in the reaction system may increase.
The addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less, based on the total amount of the modifier. If the addition ratio of bromine based on the total amount of the modifier is more than 25% by weight, the amount of generated bromic acid in the reaction system may increase. If the addition ratio is less than 1% by weight, the sterilization ability may deteriorate.
The reaction temperature at the time of bromine addition is preferably controlled to be 0 ℃ or more and 25 ℃ or less, and from the viewpoint of production cost and the like, it is more preferably controlled to be 0 ℃ or more and 15 ℃ or less. When the reaction temperature is higher than 25 ℃ at the time of bromine addition, the amount of bromic acid generated in the reaction system may increase, and when the reaction temperature is lower than 0 ℃ at the time of bromine addition, freezing may occur. Examples
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples.
[ preparation of Stable hypobromous acid composition ]
Under a nitrogen atmosphere, 16.9 weight percent (wt%) liquid bromine, 10.7 wt% sulfamic acid, 12.9 wt% sodium hydroxide, 3.94 wt% potassium hydroxide, and water as the balance were mixed to prepare a stable hypobromous acid composition. The stabilized hypobromous acid composition had a pH of 14 and a total chlorine concentration of 7.5 wt%. The total chlorine concentration is a value (mg/L in Cl) measured by a total chlorine measuring method (DPD (diethyl-p-phenylenediamine) method) using a Multi-Item Water Quality Analyzer DR/4000 manufactured by HACH corporation2Meter). Details of the method of preparing the stable hypobromous acid composition are described below.
In a 2L four-necked flask filled with nitrogen gas by continuously injecting nitrogen gas while controlling the flow rate of nitrogen gas by a mass flow controller so as to maintain the oxygen concentration of 1% in a reaction vessel, 1436g of water and 361g of sodium hydroxide were added and mixed, then 300g of sulfamic acid was added, the resulting mixture was mixed, then 473g of liquid bromine was added while keeping cooling, the temperature of the reaction liquid was made 0 to 15 ℃, 230g of a 48% potassium hydroxide solution was further added to obtain a desired stable hypobromous acid composition (composition 1) in which the contents of sulfamic acid and bromine were 10.7% and 16.9%, respectively, in terms of weight ratio to the total amount of the composition, and the ratio of the equivalents of sulfamic acid to the equivalents of bromine was 1.04. The pH of the resulting solution was 14, as measured by the glass electrode method. The bromine content of the resulting solution, determined by converting bromine to iodine with potassium iodide, was 16.9%, and then a redox titration was carried out using sodium thiosulfate, the bromine content being 100.0% of the theoretical content (16.9%). Further, the Oxygen concentration in the reaction vessel during the reaction of bromine was measured by using "Oxygen Monitor JKO-02LJD 11" manufactured by JICKO Ltd. The concentration of bromic acid is less than 5 mg/kg.
The pH was measured under the following conditions.
Electrode type: glass electrode type
A pH meter: model IOL-30 manufactured by DKK-TOA
Electrode calibration: two-point calibration was performed using a neutral phosphate pH (6.86) standard solution (type 2) and a borate pH (9.18) standard solution (type 2), each manufactured by kanto chemical co.
Measuring the temperature: 25 deg.C
Measurement values: the electrode was immersed in the measurement liquid, the stable value was defined as the measurement value, and the average value of three measurements was used.
< example 1>
Raw water (20 m) containing 3ppm isopropyl alcohol (IPA) was treated by a reverse osmosis membrane treatment system shown in FIG. 13H). The recovery rate in the first reverse osmosis membrane treatment was set to 75%, and the recovery rate in the second reverse osmosis membrane treatment was set to 90%. As the reverse osmosis membrane, 8 inches of the spirally wound membrane was used, and the number of membranes in each of the first stage and the second stage was 10. For the first reverse osmosis membrane treatment, "ES 20-D8" (manufactured by Nitto electrician; permeate flux per 1MPa of effective pressure: 1.14 m)3/m2D) as a reverse osmosis membrane, and for the second reverse osmosis membrane treatment, "SWC 5 MAX" (manufactured by Hydranautics corporation; permeate flux per 1MPa effective pressure: 0.32m3/m2And/d) as a reverse osmosis membrane. The results are shown in Table 1.
The permeate flux per 1MPa effective pressure was calculated based on the values in the specification table from each membrane manufacturer. For the reverse osmosis membrane without the specification table, the permeate flux was calculated based on the average operating pressure, the amount of permeate water, and the raw water quality obtained by measuring the indicated value on the measuring instrument connected to the second reverse osmosis membrane device.
< example 2>
For the first stage of reverse osmosis membrane treatment, "ES 20-D8" was used as the reverse osmosis membrane, and for the second stage of reverse osmosis membrane treatment, "SWC 5 MAX" was used as the reverse osmosis membrane. The rejection improving treatment (modification treatment) is performed on the second reverse osmosis membrane by the following method. Except for this, the same operation procedure as in example 1 was carried out to carry out reverse osmosis membrane treatment. The results are shown in Table 1.
[ rejection improvement treatment ]
Water containing 10ppm of the stabilized hypobromous acid composition as a retention improver (modifier) was passed at an operating pressure of 2.0MPa, pH 4, and water temperature 25 ± 1 ℃. When the permeation flux of the treated membrane per 1MPa of effective pressure reaches 0.2m3/m2When/d, the process is ended.
< comparative example 1>
"ES 20-D8" was used for both the first reverse osmosis membrane treatment and the second reverse osmosis membrane treatment. The rejection improving treatment (modification treatment) is performed on the second reverse osmosis membrane by the following method. Except for this, the same operation procedure as in example 1 was carried out to carry out reverse osmosis membrane treatment. The results are shown in Table 1.
[ rejection improvement treatment ]
The total circulation operation using water containing 1ppm of polyethylene glycol (weight average molecular weight MW ═ 5000) as a retention improver (modifier), and returning the total amount of concentrated water and permeated water to the feed water was performed at an operating pressure of 1MPa, a pH of 7, and a water temperature of 25 ℃ for 12 hours. The permeation flux per 1MPa effective pressure of the treated membrane was 1.0m3/m2/d。
< comparative example 2>
Except that "ES 20" (manufactured by Nitto electrician; permeation flux per 1MPa of effective pressure: 1.14 m) was used3/m2The reverse osmosis membrane treatment was carried out by carrying out the same operation as in example 1 except that it was used as a second reverse osmosis membrane. The results are shown in Table 1.
< comparative example 3>
Except that "LFC 3-LD" (manufactured by Hydranautics; permeation flux per 1MPa effective pressure: 0.79 m)3/m2The reverse osmosis membrane treatment was carried out by carrying out the same operation as in example 1 except that it was used as a second reverse osmosis membrane. The results are shown in Table 1.
TABLE 1
Figure BDA0002043845350000191
In the treatment methods of examples, the permeated water had a lower IPA concentration and a higher water quality than those in the comparative examples. In addition, by using the stable hypobromous acid composition as a modifier, the water quality is further improved.
< example 3>
A reverse osmosis membrane modified by the method in example 2 was used for the second reverse osmosis membrane treatment, and water was passed through for 1000 hours while adding a stable hypobromous acid composition at the inlet in the second reverse osmosis membrane treatment. The stabilized hypobromous acid composition was added in such a manner that the total chlorine concentration of the concentrated water in the second reverse osmosis membrane treatment was 1.0(mg/L, as Cl)2Meter). Other water passing conditions were the same as in example 2. The results are shown in Table 2.
< example 4>
A reverse osmosis membrane modified with hypochlorous acid as a modifier was used, and water was passed through in the same manner as in example 3. The modification conditions were the same as in example 2, except that the modifier was changed to hypochlorous acid. The permeate flux per 1MPa effective pressure in the treated membrane was 0.2m3/m2And d. The reverse osmosis membrane modified with hypochlorous acid was used for the second reverse osmosis membrane treatment, and water was passed through for 1000 hours while adding hypochlorous acid at the inlet in the second reverse osmosis membrane treatment. Hypochlorous acid was added in such a manner that the total chlorine concentration of the concentrated water in the second reverse osmosis membrane treatment was 1.0(mg/L, in Cl)2Meter). Other water passing conditions were the same as in example 2. The results are shown in Table 2.
TABLE 2
Figure BDA0002043845350000201
Comparison of the IPA concentration of the permeate water in the second stage reverse osmosis membrane treatment after 1000 hours of operation time shows: there was little change in example 3, while the IPA concentration increased in example 4. This is considered to be because the stabilized hypobromous acid composition has less influence on the deterioration of the reverse osmosis membrane than hypochlorous acid, and therefore, the membrane deterioration can be suppressed even if the modification is performed for a long time.
Therefore, according to the method in the examples, a sufficient water quality improvement effect is obtained in the reverse osmosis membrane treatment system and the treatment method in which treatment is performed by a reverse osmosis membrane in two or more stages.
List of reference numerals
1 reverse osmosis membrane treatment system
3 Water treatment system
10 treatment target water tank
12 first reverse osmosis membrane treatment device
14 second reverse osmosis membrane treatment device
16 pump
18 treating the target Water pipe
20 treatment target water supply pipe
22 first permeate pipe
24 first concentrated water pipe
26 second water penetration pipe
28 second concentrate pipe
30. 30a, 30b, 30c, 30d, 30e, 30f oxidizing agent addition tubes
50 pretreatment system
52 pretreatment water tank
54 raw water supply pipe
56 pretreatment water pipe
58 pre-treatment water supply pipe

Claims (10)

1. A reverse osmosis membrane treatment system comprising:
a first reverse osmosis membrane treatment unit for passing treatment target water through a first reverse osmosis membrane to obtain first permeate water and first concentrate water; and
at least one second reverse osmosis membrane treatment unit for passing the first permeate water through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water, wherein
The permeate flux per 1MPa effective pressure in the second reverse osmosis membrane is lower than the permeate flux per 1MPa effective pressure in the first reverse osmosis membrane, and the permeate flux in the second reverse osmosis membrane isHas a permeation flux of 0.5m per 1MPa effective pressure3/m2(ii) a ratio of (c)/(d) or less,
the permeate flux per 1MPa effective pressure of the second reverse osmosis membrane is in the range of 10% to 60% of the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane.
2. The reverse osmosis membrane treatment system of claim 1, wherein the second reverse osmosis membrane is a membrane modified with an oxidizing agent.
3. The reverse osmosis membrane treatment system of claim 2, wherein an oxidant addition unit is provided between the first reverse osmosis membrane treatment unit and the second reverse osmosis membrane treatment unit.
4. A reverse osmosis membrane treatment system according to claim 1 wherein the second reverse osmosis membrane is a membrane modified with at least one of a stabilized hypobromous acid composition comprising a bromine-based oxidizing agent and a sulfamic acid compound and a stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and a sulfamic acid compound.
5. A reverse osmosis membrane treatment system according to claim 1 or 2, wherein the treatment target is at least one of boron-containing water and low molecular weight organic substances having a molecular weight of 200 or less.
6. A reverse osmosis membrane treatment process comprising:
a first reverse osmosis membrane treatment step of passing treatment target water through a first reverse osmosis membrane to obtain first permeate water and first concentrate water; and
at least one second reverse osmosis membrane treatment step for passing the first permeate water through a second reverse osmosis membrane to obtain a second permeate water and a second concentrate water, wherein
The second reverse osmosis membrane has a lower permeate flux per 1MPa of effective pressure than the first reverse osmosis membraneA permeate flux per 1MPa effective pressure in the permeable membrane and a permeate flux per 1MPa effective pressure in the second reverse osmosis membrane of 0.5m3/m2(ii) a ratio of (c)/(d) or less,
the permeate flux per 1MPa effective pressure of the second reverse osmosis membrane is in the range of 10% to 60% of the permeate flux per 1MPa effective pressure of the first reverse osmosis membrane.
7. A reverse osmosis membrane treatment process according to claim 6 wherein said second reverse osmosis membrane is a membrane modified with an oxidizing agent.
8. The reverse osmosis membrane treatment process of claim 7 wherein an oxidant addition step is included between the first reverse osmosis membrane treatment step and the second reverse osmosis membrane treatment step.
9. A reverse osmosis membrane treatment process according to claim 6 wherein the second reverse osmosis membrane is a membrane modified with at least one of a stabilized hypobromous acid composition comprising a bromine-based oxidizing agent and a sulfamic acid compound and a stabilized hypochlorous acid composition comprising a chlorine-based oxidizing agent and a sulfamic acid compound.
10. A reverse osmosis membrane treatment method according to claim 6 or 7, wherein the treatment target is at least one of boron-containing water and low molecular weight organic substances having a molecular weight of 200 or less.
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